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Carbonized Lignin as Sustainable Filler in Biobased

Poly(trimethylene terephthalate) Polymer for Injection Molding
Applications
Petri Myllytie,† Manjusri Misra,‡,† and Amar K. Mohanty*,‡,†
†
Bioproducts Development and Discovery Centre (BDDC), Crop Science Building, Department of Plant Agriculture, University of
Guelph, 50 Stone Road East, Guelph, N1G 2W1 Ontario, Canada
‡
School of Engineering, Thornbrough Building, University of Guelph, 50 Stone Road East, Guelph, N1G 2W1 Ontario, Canada
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ABSTRACT: Light weight and sustainability are the key drivers in

the development of novel biobased thermoplastic compounds for
automotive applications. This paper reports the engineering
properties of thermoplastic compound consisting of a novel
Downloaded via 196.191.221.208 on August 13, 2023 at 22:06:20 (UTC).

bioresourced carbon filler in combination with partially biobased

poly(trimethylene terephthalate). The bioresourced carbon filler,
which was derived from lignin residue of cellulosic ethanol
production, has a clear advantage in terms of density compared to
glass fiber and other minerals, and shows potential for weight
reduction with 7% lower density at 20% filler content. Polymer
processing conditions were optimized in terms of thermomechan-
ical properties, and use of a reactive chain extender additive was
studied for improving the performance of the compound. At the
optimized conditions, good dimensional stability, 89% increase in
heat deflection temperature, 60% increase in flexural modulus, and 14% increase in flexural strength was attained in comparison
to neat PTT polymer. Theoretical modeling based on a rule-of-mixture approach showed good agreement of the predicted and
experimental modulus of the studied composites. When compared to existing mineral filled engineering polyester resin, many
properties of the prepared compounds were on a comparable or favorable level, indicating good potential of the bioresourced
carbon filler for light weighting and highly sustainable engineering applications.
KEYWORDS: Lignin, Biomass valorization, Thermal conversion, Filled plastics, Biopolymers, Biocomposites, Injection molding

■ INTRODUCTION
The automotive industry is one of the largest users of
other lightweight materials will remain in the focus of the
industry for years to come.2
Most of the engineering plastics originate from non-
engineering plastics. The use of plastics and composites has
renewable petroleum based feedstock, and the sustainability
been steadily increasing in strive for weight reduction,
benefits of using engineering plastics include improved fuel
improved passenger comfort, and safety features that typically
economy as well as reusability and recyclability of the plastic
deploys advanced design and engineering resins to maximize parts. Engineering plastics from renewable and sustainable
the technical performance while providing economically viable resources are getting more and more of a foothold in the
mass production by injection molding. Weight reduction by market, but the price premium of the renewable feedstock
advanced and innovative uses of engineering plastics is one of chemicals typically limits the use to niche applications instead
the most important attributes for automotive industry to use of large volume manufacturing where price is a crucial property,
and develop new applications for engineering plastics.1,2 The if technical properties are at par level. In some cases, the
global commitment for reduction of greenhouse gases (GHG’s) renewably resourced chemical feedstock is readily competitive
has placed legislative pressure on the automotive industry to with the petroleum based counterpart. One example is
improve the fuel economy and reduce the emissions of new and poly(trimethylene terephthalate) (PTT) polymer, which is a
future vehicles. In the US, targets have been set for the partly biobased thermoplastic engineering polyester commer-
corporate average fuel economy (CAFE) whereas in Europe the cialized by DuPont (Wilmington, DE, USA). The biobased
targets are for the amount of CO2 emissions per kilometer per ingredient of the PTT polymer is 1,3-propanediol (PDO)
average vehicle produced.2,3 Because weight reduction turns
directly into savings in fuel economy, and reduced overall Received: August 1, 2015
weight helps in down gauging other components in a vehicle, a Revised: September 27, 2015
spiral of light weighting is created, and plastics, composites and Published: December 16, 2015

© 2015 American Chemical Society 102 DOI: 10.1021/acssuschemeng.5b00796

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obtained from an industrial scale fermentation process.4 As an the potential against the established material solutions in the
engineering plastic, in terms of technical properties, the PTT plastics market.

■
competes with two other polyesters, PET and PBT, which are
widely used for example in automotive applications. In terms of EXPERIMENTAL SECTION
sustainability, the partly biobased PTT with 37% renewable
Materials. The partly biobased thermoplastic engineering polyester
content clearly outperforms the PET and PBT polyesters while
poly(trimethylene terephthalate), Sorona PTT, was obtained from
providing a comparable level of technical performance.5,6 DuPont (Wilmington, DE, USA). The polymer was dried overnight in
Injection molded glass fiber reinforced PTT composites have an air circulation oven at 105 °C prior to processing. The lignin
been thoroughly characterized and successfully introduced as residue of bioethanol production was received from Mascoma
sustainable, high performance materials for automotive interior (Brampton, ON, Canada). The lignin residue was stored frozen and
applications.7,8 the moisture content of the material was around 47−51%. The lignin
For optimal end use performance, engineering plastics are material has been characterized earlier and it consisted mainly of lignin
often compounded with mineral fillers and glass and/or carbon and crystalline cellulose.18 Reactive epoxy functional polymeric chain
fibers. Mineral fillers like talc, calcium carbonate, and mica extender (CE) used was Joncryl 4368 manufactured by BASF (BASF,
improve stiffness, thermal properties, and economics of the Ludwigshafen, Germany).
engineering plastics but the high density of 2.4−2.8 g/cm3 of Thermal Conversion of Lignin. The frozen lignin residue of
bioethanol production was dried in an air circulating oven at 105 °C.
the minerals, and glass fibers as well, adds to the weight of the After drying, the material was pulverized in a Retsch PM100 planetary
materials.9 Therefore, when designing new plastic parts for ball mill (Retsch GmbH, Haan, Germany). The dry lignin residue was
engineering applications and assigning new materials for pulverized by ball milling with two 40 mm diameter steel balls at 250
specified end uses, in some cases it is important to evaluate rpm for 2 h. The pulverized lignin was transferred into ceramic
the specific stiffness and strength, i.e., to calculate the stiffness crucibles and Carbolite (Hope Valley, UK) GHA horizontal tube and
and strength divided by density. Materials with high specific Carbolite VST vertical tube furnaces were used for the thermal
properties are preferred for light weighting purposes and are conversion process. The conditions of the thermal conversion process,
widely used in aerospace applications where lightweight is which was essentially a slow pyrolysis under nitrogen gas atmosphere,
crucial. As the price per performance of the high performance had been optimized in an earlier work.14,17 The heating ramp rate,
materials gradually reduce with increasing applications and isothermal temperature, and dwell time at the isothermal temperature
for the thermal conversion were 20 °C/min, 900 °C, and 6 h,
market volumes, the materials will find their way to more cost
respectively. Continuous flow of nitrogen was used to purge the tube
sensitive high volume applications, like automotive. Because of furnaces during the thermal conversion process including the cooling
the high density of minerals, mineral filled engineering plastics phase. The product of the thermal conversion process was a porous
may not be the best way to reach high specific properties for solid carbonaceous material, which was pulverized by ball milling with
the plastic compound. Therefore, it is justified to research and two 40 mm diameter steel balls at 250 rpm for 2 h. The pulverized
develop lower density fillers that could improve the specific carbonaceous material was then characterized by elemental analysis,
properties of filled plastics. Hollow glass spheres and mineral functional group analysis, and sieve analysis. The pulverized
tubes are good examples of low density fillers for plastics, but carbonaceous material was subsequently used without further
the higher cost is likely to limit the applications.10,11 PTT has modification as sustainably sourced low density filler for the partly
previously been used in composites with carbon nanotubes and biobased thermoplastic poly(trimethylene terephthalate) polymer.
Characterization of the Carbon Filler. Elemental composition
carbon fibers;12,13 however, the present study involving PTT
of the sustainably sourced carbon filler was measured by Thermo
composites with carbonized lignin is the first of this type. Scientific (Waltham, MA, USA) Flash 2000 analyzer, capable of
Recently, a renewably sourced carbon material was determining elemental carbon (C), hydrogen (H), nitrogen (N), sulfur
introduced as a sustainable alternative to petroleum based (S), and oxygen (O). The C, H, N, and S elements were measured
black pigment commonly used in plastics.14 The sustainable against known calibration sample of 2,5-bis(5-tert-butyl-2-benzoxazol-
alternative for carbon black pigment was derived from the yl) thiophene (BBOT). Fourier transform infrared spectroscopy
lignin residue of second generation bioethanol production. The (FTIR) was performed with Thermo Scientific Nicolet 6700 FT-IR
sustainable nature of bioresourced carbonaceous materials has spectrometer in attenuated total reflectance (ATR) mode using
been studied in depth, and pyrolyzed biomass is identified as a diamond ATR crystal. FTIR spectra were recorded with resolution of 4
viable method of carbon sequestration and greenhouse gas cm−1 and 64 scans per sample. Particle size fractions of the carbon
reduction.15,16 Current studies have analyzed the use of filler were evaluated by sieving the material through a 20 μm sieve. A
Retsch AS 200 air jet sieving machine (Retsch GmbH, Haan,
biocarbon as a soil amendment; the use of biocarbon in Germany) was used for the sieving, and sample size and sieving time
composite materials provides another novel application that were 2 g and 10 min, respectively.
allows for carbon sequestration. The lignin residue was Processing of PTT and Carbon Filled PTT Compounds.
thermally converted into carbonaceous material with relatively Laboratory scale extrusion and injection molding equipment, DSM
high elemental carbon content and mechanically processed to a Xplore from DSM (Heerlen, Netherlands), was used in processing and
size range suitable for compounding with plastics.14,17 The aim preparation of tensile, flexural, and impact test specimens. Neat PTT
of this work was to study the use of the renewably sourced and PTT containing 20% of carbon filler with and without chain
biobased carbon material as low density filler in partly biobased extender additive were extruded and injection molded at selected
thermoplastic polyester matrix. Laboratory scale extrusion and processing conditions. 0.4% of chain extender by weight was
injection molding was used for preparation of the compounds incorporated into the corresponding blends. Melt temperature and
barrel temperature were set to 250 °C, mixing time in the twin-screw
and molded samples, followed by mechanical, thermal, extruder was 2 min and screw speed was 100 rpm. Mold temperature
thermomechanical, and morphological characterization of the was varied between 30 and 100 °C in order to find balance between
prepared materials. Material properties were reported and mechanical and thermal performance of the PTT polymer. After initial
complemented by comparison to theoretical model of thermo- testing, the studied compositions were processed at mold temperature
plastic composite materials. Specific attention was paid to the of 80 °C. The injection parameters were adjusted to get properly filled
engineering characteristics of the material in order to evaluate parts without short shots, sink marks, or excessive flash, and the

103 DOI: 10.1021/acssuschemeng.5b00796

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Figure 1. (a) DSC first heating curves, and (b) TMA thermal expansion curves for neat PTT molded at different mold temperatures.

Figure 2. Notched Izod impact strength and heat deflection temperature of (a) neat PTT at different mold temperatures, and (b) neat PTT with
increasing amount of chain extender at constant mold temperature of 80 °C.

parameters varied slightly depending on the composition of the melt heating rate of 2 °C/min. Span length of the sample was 50 mm and
and the specimen molded. the applied force was calculated to match the 0.455 MPa stress
Mechanical Characterization of PTT and Carbon Filled PTT according to ASTM D648 standard. Heat deflection temperature was
Compounds. Tensile, flexural, and impact properties of the PTT and taken as the temperature where the strain reached the value specified
carbon filled PTT composites were measured according to standards by the standard. Thermal expansion of the materials was measured
ASTM D638, D790, and D256, respectively. Tensile and flexural test with TMA in temperature range from 30 to 130 °C with heating rate
were performed with Instron 3382 Universal Testing Machine of 5 °C/min. Some of the samples exhibited large change of
(Instron, High Wycombe, UK). Tensile tests were performed at dimensions near the glass transition temperature and thermal
deformation rate of 5 mm/min and flexural tests were carried out at expansion values were determined both below and above glass
deformation rate of 1.4 mm/min. A TMI 43-02 Monitor Impact transition temperature. Because of the chosen sample geometry, the
Tester (Testing Machines Inc., New Castle, DE, USA) with 0−5 × coefficient of linear thermal expansion (CLTE) was measured
0.05 ft·lbs standard impact hammer was used to measure notched Izod perpendicular to the melt flow direction. All reported CLTE values
impact strength. were determined at the linear regions of 35−50 °C and 80−120 °C,
Thermal and Thermomechanical Testing. A differential below and above the glass transition of the PTT polymer.
scanning calorimetry (DSC) Q200 from TA-Instruments (New Morphology and Density of the Materials. Fracture surfaces of
the notched impact test pieces were imaged with an FEI (Hillsboro,
Castle, DE, USA) was used for thermal characterization of the
OR, USA) Inspect S50 scanning electron microscopy (SEM)
materials. Thermal transitions including glass transition temperature
instrument using 20 kV acceleration voltage. Prior to imaging, the
(Tg), melting and crystallization temperatures, and associated changes samples were sputter coated with gold. Density of the materials was
in enthalpies were measured with DSC. The DSC measurements were measured by displacement method according to ASTM D792 using
performed in heat/cool/heat cycles between 0 and 250 °C using a Alfa Mirage MD300 densimeter (Alfa Mirage Co., Ltd., Osaka, Japan).

■
heating rate of 10 °C/min and cooling rate of 5 °C/min. A dynamic
mechanical analyzer (DMA) Q800 and thermomechanical analyzer
(TMA) Q400 from TA Instruments were used for thermomechanical
RESULTS AND DISCUSSION
characterization of the materials. Heat deflection temperature of the Optimization of Mold Temperature for PTT Process-
samples was determined with DMA in three point bending mode at ing. Semicrystalline engineering plastics, such as PTT and PBT
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Table 1. Tensile and Flexural Properties of Poly(trimethylene terephthalate) PTT and 20% Bioresourced Carbon Filled PTT
Composites with and without Chain Extender (CE) Molded at 80 °C Mold Temperature
material Et, MPaa σY, MPa εY, % Ef, MPa σf, MPa
PTT 2630 (48) 59.1 (0.7) 4.3 (0.3) 2669 (20) 98.2 (1.0)
PTT + 0.1% CE 2720 (29) 60.0 (0.6) 3.7 (0.1) 2695 (36) 100.7 (1.5)
PTT + 0.2% CE 2840 (57) 61.7 (0.7) 5.2 (1.0) 2800 (27) 103.9 (1.1)
PTT + 0.4% CE 2870 (38) 65.1 (0.6) 8.8 (0.3) 2884 (32) 102.6 (0.6)
PTT + 20% carbon filler 4210 (127) 62.0 (0.9) 2.2 (0.1) 4327 (63) 103.2 (1.4)
PTT + 20% carbon filler, 0.4% CE 4290 (66) 62.0 (2.5) 2.2 (0.4) 4273 (23) 112.1 (0.9)
a
Symbols: Et, σY, εY, Ef, and σf denote tensile modulus, tensile strength, yield elongation, flexural modulus, and flexural strength, respectively.
Standard deviation for each measurement is given in parentheses.

and polyamides 6 and 6.6, are typically molded with elevated narrow temperature range around the Tg of the polymer. Only
mold temperatures whereas polyethylene and polypropylene at mold temperatures of 80 °C and above does the trend in
can be molded with cold mold due to faster crystallization.19 thermal expansion become fairly linear through the measure-
Optimum mold temperature depends on the application and ment range of 30−130 °C. The CLTE of PTT below Tg
the product attributes, like surface quality. For molded technical reduced with higher mold temperatures whereas above Tg the
parts made of polyesters and polyamides, high crystallinity is CLTE slightly increased compared to low mold temperatures.
needed to ensure good mechanical and thermo-mechanical The CLTE values of PTT measured below Tg were in the range
performance, whereas amorphous polymer structure can be of 6.5−7.9 × 10−5 1/°C and above Tg in the range of 1.3−1.7 ×
useful in film applications. In this work, the aim was to evaluate 10−4 1/°C. In comparison to previously reported values for
the applicability of renewably sourced carbon material as low PTT (4.1 × 10−5 and 1.4 × 10−4 1/°C below and above Tg,
density filler in technical molded parts, and the first step was to respectively),24 the obtained values above Tg were similar,
find optimum mold temperature for the experiments. Process whereas below Tg the measured CLTE values were somewhat
optimization was conducted based on the lab scale processing higher. Difference may arise from measurement direction,
equipment used in this study. Figure 1a shows DSC first which was not stated, and from different grade of PTT used in
heating curves, and Figure 1b shows TMA thermal expansion of the study.24 The observed large transition in a narrow
neat PTT molded at different mold temperatures. At a low temperature range in the low mold temperature samples
mold temperature of 40 °C, the polymer exhibits cold (Figure 1b) can be considered a risk in terms of end-use
crystallization transition between 50 and 75 °C (Figure 1a). performance. From a part design and manufacturing
Higher mold temperature promotes the crystallization of the perspective, it is essential that the thermomechanical properties,
polymer and already at 60 °C mold temperature the cold like HDT and CLTE are known and predictable. Therefore, the
crystallization transition is considerably decreased. With further mold temperature of 80 °C was considered optimal for the
increase of the mold temperature to 80 and 100 °C, the cold purpose of this study.
crystallization was not observed anymore (Figure 1a). The Use of Chain Extender To Improve the Properties of
obtained DSC results correlated well with earlier injection PTT. Polyester thermoplastics are typically sensitive to
molding studies of PTT polymer.20 The neat PTT molded at moisture, and despite of proper drying prior to processing
different mold temperatures was also evaluated by impact and hydrolysis can occur in melt processing causing reduction of
heat resistance and thermomechanical analysis because the molecular weight and mechanical performance. Reactive chain
properties were known to be sensitive to the mold temper- extenders are particularly useful in processing of recycled
ature.21,22 Figure 2a shows the notched Izod impact strength plastics where degradation occurs due to moisture, contami-
and HDT of the neat PTT at different mold temperatures. The nants, and increasing number of melt processing cycles.25 Chain
impact strength of neat PTT (Figure 2a) shows a decrease extenders can help to maintain the molecular weight and
between the mold temperatures of 40 and 60 °C. The balance the viscosity and mechanical properties of PTT already
reduction in the impact strength can be related to the in the first melt processing cycle.26 Because the objective of this
crystallization of PTT at 60 °C and above, and it correlates work was to develop compounds as intermediate products for
with the disappearance of the cold crystallization transition in further processing, such as injection molding of technical parts,
the DSC results (Figure 1a). The HDT of neat PTT molded it was justified to explore the effect of chain extender additive
with 40 °C mold is low, only about 46 °C, whereas the HDT at on the PTT properties in order to find the optimum level of
mold temperatures of 80 and 100 °C is 99 and 117 °C, addition for the subsequent compounding experiments. Figure
respectively. The relatively low HDT of neat PTT molded with 2b presents the impact and thermal resistance and Table 1
cold mold is in accordance with earlier studies.21−23 Because of comprises the tensile and flexural properties of PTT modified
quick cooling in a cold mold, the PTT polymer remains with reactive chain extender additive. The studied addition
amorphous to a high extent and there is not much crystalline levels were limited below 0.5% to avoid gel formation by cross-
structure to contribute to the mechanical resistance at linking as reported in an earlier study about long-chain
temperatures above glass transition. Indeed, a considerable branching of PTT.27 The addition of chain extender to neat
decrease in storage modulus has been observed by DMA in the PTT in the first processing cycle caused only minor
neat PTT above the glass transition temperature (Tg) in the improvements on the tensile and flexural properties (Table
earlier reports on PTT composites where low mold temper- 1) and the largest increase was observed in the thermal
ature was applied.21,22 In terms of thermal expansion (Figure resistance, as evidenced by the HDT results (Figure 2b).
1b), the low mold temperature samples (40 and 60 °C) show Addition of fillers in thermoplastics typically decreases the
large transitions, both expansion and contraction, within a ductility and elongation at yield of the materials. In the case of
105 DOI: 10.1021/acssuschemeng.5b00796
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neat PTT, the highest level of chain extender (0.4% addition) produced a particle size that is within the range of typical
increased the elongation at yield as much as 105% (Table 1). mineral fillers used in plastics compounding.9,29
Therefore, to counterbalance the decrease in yield elongation Mechanical Properties of the Bioresourced Carbon
and ductility by filler addition, it was considered worthwhile to Filled PTT Composites. Figure 4 presents the impact and
test the 0.4% addition level of the chain extender in the
subsequent compounding experiments of PTT with the
bioresourced carbon filler.
Properties of the Bioresourced Carbon Filler. FTIR
analysis was done on the bioresourced carbon filler used in the
compounding experiments. Because the material was prepared
by thermal conversion at high temperature, 900 °C for 6 h
under nitrogen atmosphere, it was expected that very little
functionality would be seen in the FTIR spectra, as reported
earlier.14 Figure 3 shows FTIR spectra of bioresourced carbon

Figure 4. Notched Izod impact strength and heat deflection

temperature of neat PTT and 20% bioresourced carbon filled PTT
composites with and without chain extender (CE) at constant mold
temperature of 80 °C.

thermal resistance, and Table 1 contains the tensile and flexural

properties of the prepared PTT composites filled with 20% of
sustainably sourced low density carbon filler in the absence and
Figure 3. FTIR-ATR spectra of lignin raw material and of the presence of reactive chain extender. The decrease in impact
bioresourced carbon fillers prepared in horizontal and vertical tube performance (Figure 4) and the reduction in yield elongation
furnaces. compared to neat PTT (Table 1) points out increased
brittleness by incorporation of the carbon filler into the PTT
matrix. The less ductile impact failure is also evidenced in the
filler prepared in the horizontal and vertical tube furnaces SEM images comparing the crack initiation points of neat PTT
together with spectra of the lignin raw material. The observed and 20% carbon filled PTT composite, presented in Figure 5.
peaks in the carbon filler spectra are relatively small and hard to
resolve, indicating considerable reduction in chemical func-
tional groups during the thermal conversion. The FTIR spectra
of the bioresourced carbon filler prepared with both horizontal
and vertical tube furnaces are similar to very high extent,
demonstrating that the carbonization conditions (900 °C for 6
h under nitrogen atmosphere) were comparable between the
furnaces. The elemental analysis results of the bioresourced
carbon filler, shown in Table 2, showed quite high carbon Figure 5. SEM images of impact fracture surfaces of (a) neat PTT and
content of 88%, which is well in agreement with the SEM-EDS of (b) and (c) 20% bioresourced carbon filled PTT composite.
results reported earlier.14 The high carbon content was
expected based on studies of high temperature pyrolysis of
lignocellulose materials under inert nitrogen atmosphere.28 The appearance and topography of the fracture surface is very
Furthermore, the particle size fractions of the carbon filler were different in the 20% carbon filled PTT composite (Figure 5b)
evaluated by air jet sieve analysis. It was found that 99% of the in comparison to neat PTT (Figure 5a). The deep grooves and
carbon filler particles passed through the 20 μm sieve, plastic deformation in the fracture surface of the neat PTT
confirming that the pulverization by ball milling efficiently (Figure 5a) are not present when the polymer is filled with 20%

Table 2. Elemental Carbon (C), Hydrogen (H), Nitrogen (N), Sulphur (S), and Oxygen (O) Content of Pulverized
Bioresourced Carbon Filler Determined by CHNS-O and SEM-EDS Techniques
sample method C, % H, % N, % S, % O, %
bioresourced carbon filler CHNS-O 87.8 (0.9) 0.32 (0.01) 0.86 (0.07) 0
carbonized lignina SEM-EDS 90.2 (1.4) 9.8 (1.4)

a
Literature reference values.14 Standard deviation for each measurement is given in parentheses.

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Figure 6. (a) DSC curves at first cooling and (b) DSC curves at 2nd heating of neat PTT and 20% bioresourced carbon filled PTT composites with
and without chain extender (CE) at constant mold temperature of 80 °C.

of carbon and the fracture surface become much smoother with composites. The addition of chain extender caused only a
less plastic deformation (Figures 5b,c). The observed difference minor increase in the HDT of the carbon filled composites
can be related to reduced ductility, and it agrees with the (Figure 4), whereas for the neat PTT, the chain extender clearly
measured impact performance. The impact strength and yield increased the HDT with increasing addition level (Figure 2b).
elongation for the 20% carbon filled PTT are practically the The substantial rise in the HDT can be ascribed both to the
same regardless of the addition of the reactive chain extender, reinforcing action of the carbon filler and to the increased
which suggests that the chain extender only improved ductility crystallinity of the PTT matrix due to nucleation effect of the
in the absence of the carbon filler (Table 1). According to the filler particles. Figure 6a shows DSC curves recorded on first
elemental and FTIR analysis of the carbon filler (Table 2, cooling, and Figure 6b shows DSC curves recorded on second
Figure 3), the high temperature thermal conversion process was heating for PTT and 20% carbon filler containing PTT
shown to produce high carbon content with little functional composites in the absence and presence of reactive chain
groups. Therefore, the carbon filler was considered to be inert extender. It is clear that the carbon filler particles advance the
without much interaction with the PTT matrix polymer. The crystallization of the PTT by acting as nucleating sites for the
only improvement in the mechanical properties of carbon filled crystallization. The crystallization peak and onset temperatures
PTT composite by the reactive chain extender addition was are shifted toward higher temperature (Figure 6a). The
slight increase in the flexural strength of about 9% compared to nucleation effect of the carbon filler is more pronounced in
the composite without chain extender, and no improvement in the absence of the chain extender, and the crystallization peak
yield elongation was observed, in contrast to the effect of chain temperature is 201 °C compared to the value of 182 °C of the
extender on the neat PTT (Table 1). Addition of 20% of the neat PTT. The combined effect of the carbon filler and the
bioresourced carbon filler considerably increased the tensile chain extender falls between the two with crystallization peak
and flexural modulus of the composites. Tensile modulus temperature of 195 °C (Figure 6a). It is plausible that the
increased from 2.6 GPa of the neat PTT to 4.2−4.3 GPa of the reactive chain extender suppresses the nucleation effect of
20% carbon filled PTT composite, and flexural modulus carbon particles because of long chain branching of the polymer
similarly from 2.7 to 4.2−4.3 GPa. It is known that particulate chains, which reduces chain mobility and creates segments that
mineral fillers typically increase stiffness and reduce ductility are not capable to fold into crystallites, as opposed to the linear
while strength can remain unaffected, especially when the filler polymer chains in the absence of the chain extender. The effect
has low interaction with the polymer matrix.9 In many cases the of reactive chain extender on the crystallization of thermoplastic
fillers are surface treated by, e.g., surfactants and coupling polyester poly(lactic acid) has been reported earlier, and
agents in order to improve and modify the compatibility of the reduced crystallinity was observed with the use of a chain
filler with the matrix polymer used. By filler modification, it is extender.30,31 The double melting peaks in the 20% carbon
possible to counteract the reduced ductility and further filled PTT composites (Figure 6b) support the observed
improve the thermal and mechanical performance of the filled nucleating effect of the carbon filler (Figure 6a). Likely, the
polymer composites.9,29 The bioresourced carbon filler used in formed crystallites at the polymer−particle interface are
this study was considered chemically inert with low interaction different from the bulk crystallites, leading to the formation
or compatibility with the PTT polymer matrix, thus leaving of the minor peak at lower temperature than the major peak of
opportunities for improvement of the stiffness-toughness the neat PTT (Figure 6b). The degree of crystallinity for the
balance by filler−matrix interphase modification. three samples was calculated based on the crystallization peak
Thermomechanical and Thermal Properties of the of the first cooling. The crystallinities of neat PTT, PTT with
Bioresourced Carbon Filled PTT Composites. The most 20% carbon filler, and PTT with 20% carbon filler and 0.4%
prominent effect of the 20% addition of carbon filler into the chain extender were 35.3%, 36.8%, and 35.9%, respectively. The
PTT matrix was a considerable increase of HDT from 99 °C of increase of crystallinity in the 20% carbon filled PTT confirms
the neat PTT to 180−187 °C of the 20% carbon filled PTT the nucleating effect of the filler particles. Moreover, the
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presence of chain extender slightly reduced the crystallinity of modulus is considered to be rather insensitive to particle size,
the 20% carbon filled PTT, which lends support to reduced especially in the absence of strong filler−matrix interactions,
chain mobility and formation of branched or cross-linked whereas particle shape and aspect ratio, and possible
segments not capable of forming crystallites, as a contrast to the orientation during processing will have more influence on the
linear polymer chains.30,31 Overall, the measured crystallinity modulus.9 Again, the agreement with the theoretical model is
values for PTT were in agreement with previous studies.22,23 considered promising, while justifying future research work on
Figure 7 presents the thermal expansion measured by TMA for interfacial engineering of the bioresourced carbon filler to
broaden the attainable range of properties for engineering
applications.
Benchmarking against Commercial Mineral Filled
Engineering Thermoplastic. To evaluate the potential of
the compound containing 20% renewably sourced carbon filler
in the PTT polymer matrix, it is useful to compare the material
properties against existing and established engineering resin,
such as 20% mineral filled PBT/PET compound commonly
used in automotive applications.33,34 Table 3 compares the

Table 3. Property Profile of the Bioresourced Carbon Filled

Poly(trimethylene terephthalate) PTT in Comparison to
Commercial Mineral Filled Engineering Polyester
Compound
PTT + 20% commercial mineral
bioresourced filled PBT/PET
property unit carbon fillera compoundb
density g/cm3 1.38 1.49
Figure 7. TMA curves of neat PTT and 20% bioresourced carbon filler content % 20 20
filled PTT composites with and without chain extender (CE) at tensile MPa 4210 5880
constant mold temperature of 80 °C. modulus
tensile MPa 62 56
strength
neat PTT and 20% carbon filled PTT composites with and yield % 2.2 2
without chain extender. The CLTE values of 20% carbon filled elongation
PTT measured below Tg were in the range of 5.6−5.9 × 10−5 flexural MPa 4327 4680
1/°C and above Tg in the range of 1.8−2.1 × 10−4 1/°C, thus modulus
the carbon filler decreased CLTE below Tg but increased it flexural MPa 103 93
strength
slightly above Tg in comparison to neat PTT. As pointed out
Izod impact J/m 17 27
earlier in the mold temperature optimization, relatively linear strength,
thermal expansion for neat PTT was achieved above 60 °C notched
mold temperature (Figure 1b), and the TMA curves presented heat deflection °C 180 187
in Figure 7 confirm similar behavior for the 20% carbon filled temperature
composites at the mold temperature of 80 °C. The enhanced specific MPa/(g/cm3) 3136 3141
flexural
crystallization of PTT by the carbon filler could provide further modulus
opportunity for optimization of the mold temperature in terms specific MPa/(g/cm3) 75 62
of molding cycle time without adverse effects on thermal and flexural
thermomechanical performance of the composites. However, strength
that kind of study will remain outside the scope of this research. biobased % 50 0
content
Theoretical Consideration of the Bioresourced Car- a
Experimental data at 80 °C mold temperature. bDatasheet values for
bon as Filler in the PTT Matrix. The increase in modulus by
the commercial product.33,34
the 20% bioresourced carbon filler can be assessed against
theoretical models of composite materials to estimate the
efficiency of the filler addition in relation to the highest mechanical properties between the 20% carbon filled PTT and
obtainable modulus predicted by the theoretical models. On the commercial 20% mineral filled PBT/PET engineering resin.
the basis of the rule-of-mixture (ROM) approach and using The property profile of the 20% carbon filled PTT compares
modulus and density values of 2.6 GPa and 1.33 g/cm3 for the well to that of the commercial compound for most of the
matrix PTT and 12 GPa and 1.6 g/cm3 for the carbon filler,32 properties. For example, the tensile and flexural strength of the
the ROM predicts modulus of 4.1 GPa for the 20% carbon 20% carbon filled PTT exceeds the strength of the commercial
filled composite, which is in agreement with the experimental compound. Because of the lower density of the carbon filler, the
modulus of 4.2−4.3 GPa. In the above calculation, modulus of specific strength is even higher. On the other hand, the impact
the bioresourced carbon filler was assumed to be similar to strength and the tensile modulus of the 20% carbon filled PTT
anthracite coal for which the modulus is reported.32 Better are lower. In terms of flexural strength, the 20% carbon filled
estimates for the modulus are expected to be obtained as the PTT compares favorably with the commercial compound, and
research and characterization of bioresourced carbon fillers when considering the specific flexural modulus the materials are
advances in the future. Typically, fillers increase the modulus of nearly equal (Table 3). The lower density of the 20% carbon
thermoplastics linearly until around 20% by volume, and filled PTT clearly indicates the light weighting potential of the
108 DOI: 10.1021/acssuschemeng.5b00796
ACS Sustainable Chem. Eng. 2016, 4, 102−110
ACS Sustainable Chemistry & Engineering Research Article

biobased carbon filler. At 20% addition level, the carbon filler

reduces the density over 7% compared to the mineral filled
■ AUTHOR INFORMATION
Corresponding Author
counterpart, and the density difference and weight reduction *A. K. Mohanty. E-mail: mohanty@uoguelph.ca. Tel.:+1-519-
potential increases with higher filler levels. In addition to the 824-4120, ext. 56664. Fax: +1-519-836-0227.
very desired light weighting potential, the sustainably sourced Notes
biobased carbon filler adds to the biocontent of the partly The authors declare no competing financial interest.

■
biobased PTT polymer creating a composite material with 50%
biobased content, a level that only a few materials in the class of ACKNOWLEDGMENTS
thermoplastic engineering resins can currently claim, whereas The Natural Sciences and Engineering Research Council
the majority of the materials originates from nonrenewable (NSERC) Canada for the Discovery Grants (Project #
petrochemical resources. In applications where impact strength 400322); and the Ontario Ministry of Economic Development
is not critical and weight savings and sustainability are and Innovation (MEDI), Ontario Research Fund, Research
considered of prime importance, the low density biobased Excellence Round 4 (ORF-RE04) program (Project # 050231
carbon filler shows good potential. The studied composition of and 050289) are gratefully acknowledged for financial support.
20% bioresourced carbon filled PTT has, in many terms, E. I. du Pont de Nemours, Wilmington, DE, USA is
comparable or favorable property profile against commercial acknowledged for providing Sorona PTT sample.
mineral filled compound, justifying future research and
development of sustainable biobased carbon fillers for thermo-
plastic compounds and engineering applications.
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